Methods for the implementation of nanocrystalline and amorphous metals and alloys as coatings

ABSTRACT

Methods for the use of nanocrystalline or amorphous metals or alloys as coatings with industrial processes are provided. Three, specific, such methods have been detailed. One of the preferred embodiments provides a method for the high volume electrodeposition of many components with a nanocrystalline or amorphous metal or alloy, and the components produced thereby. Another preferred embodiment provides a method for application of a nanocrystalline or amorphous coatings in a continuous electrodeposition process and the product produced thereby. Another of the preferred embodiments of the present invention provides a method for reworking and/or rebuilding components and the components produced thereby.

BACKGROUND OF THE INVENTION

The present invention generally relates to methods for the practicalimplementation of nanocrystalline or amorphous metals or alloys ascoating materials. More particularly, methods of applying suchnanocrystalline or amorphous metals or alloys to high volumeelectrodeposition operations, to continuous electrodepositionoperations, and to the rebuilding and reworking of components arepresented.

Industrial applications, such as high-volume electrodepositionproduction, barrel plating, continuous electrodeposition, andrework/rebuild require coating materials with specific properties. Thereis a continual need for new and improved coating materials for theseapplications, which can offer economic benefits or improved productproperties.

High Volume Electrodeposition:

High volume electrodeposition coating processes, such as barrel plating,are economically and practically desirable for coating many componentssimultaneously. However, insufficient coating properties createsignificant challenges for these high volume electrodeposition coatingprocesses.

High volume electrodeposition processes such as barrel plating generallyinvolve more than two components being plated simultaneously, and whichcomponents may be in electrical contact with one another during at leastpart of the process. The parts may also experience contact mechanicalloads and/or abrasive loading at the electrical contact points. Suchloading may be increased if the components experience agitation duringthe process.

In design of high volume electrodeposition processes, an important issueis the character and properties of the deposited coating. In general, aweak or poorly adhered coating may be damaged by the agitation process,as components shift their relative positions and give rise to slidingcontact points or local impacts on the component surfaces. Similarly,soft and malleable coatings, or those with low hardness, low resistanceto wear, indentation, or frictional sliding damage, may acquire defectssuch as cracks, scratches or delaminations during the process. It istherefore important that the deposited coating have desirable propertiesthat resist damage during processing, and that the processcharacteristics be controlled to avoid such damage.

Another coating property of importance to the efficiency and efficacy ofa high volume electrodeposition process is its electrical conductivity.Because the electrical connection of each component to the power supplyis achieved, in general, through contacts between components or betweencomponents and the electrical lead connected to the power supply,electrical current is required to pass across the surfaces of thecomponents. As the deposition process proceeds and the components becomecoated, electrical current is required to pass through the coatingmaterial itself. If the coating is of low electrical conductivity,current flow is discouraged, reducing the efficiency of the deposition.For this reason, coatings of relatively higher electrical conductivityare generally more appropriate to high volume electrodepositionprocesses such as barrel plating.

An example relating to the electrical conductivity of electrodepositedcoatings is provided by the case of hexavalent chromium deposits.Coatings of chromium produced by deposition from the hexavalent bath aredesirable in many respects, due to the high hardness, wear resistance,and corrosion resistance of the coating. However, the electricalconductivity of hexavalent chromium coatings is low compared to manymetals, and reduces the efficiency of a high volume process such asbarrel plating. This renders such operations economically difficult tosustain.

A need has long existed for new electrodeposited coatings which combinenew suites of properties, to be produced in high volume with suchtechniques. For example, it would be desirable to use a high-strength,strong adhesion, abrasion resistant nanocrystalline or amorphous coatingwith high electrical conductivity, to improve both the quality of thecoating and coated product, as well as increase the efficiency of theprocess. Additionally desired properties include higher hardness,ductility, wear resistance, electrical properties, magnetic properties,corrosion characteristics, substrate protection, improved environmentalimpact, improved worker safety, improved cost, and many others.

Continuous Electrodeposition:

Continuous electrodeposition processes are economically and practicallydesirable for applying a coating onto a strip of material A need haslong existed for coatings being applied using continuouselectrodeposition which create a final product with more desirableproperties. For example, higher hardness, strength, ductility, wearresistance, electrical properties, magnetic properties, corrosioncharacteristics, substrate protection, improved environmental impact,improved worker safety, improved cost, and many others.

Rework/Rebuild:

Rework/rebuild processes are economically and practically desirable forcorrecting deficiencies in products. A critical step in therework/rebuild process is the application of a suitable coatingmaterial. One common material used for this coating process is hardelectrodeposited chromium, alternatively called “hard chromium” or “bardchrome”. Rework/rebuild is a common procedure for chromium platingfacilities, in which hard chromium is the material plated as a coating.Frequently, the chromium coating will be up to or in excess of 375 μm inthickness prior to the machining step. K. O. Legg cites rework andrebuild operations as comprising one of the largest single uses of hardchromium plating in his article “Overview of Chromium and CadmiumAlternative Technologies” (in Surface Modification Technologies XV,edited by T. S. Sudarshan and M. Jeandin, ASM International, MaterialsPark Ohio, 2002), which is fully incorporated herein by reference. Adrawback of hard chromium coatings for rework/rebuild operations is thetoxicity and carcinogenicity of the chemicals used in the coatingprocess, these have serious implications for the environment and forworker safety.

Other coating technologies can be applied to rework operations,including but not limited to other electroplated metal technologies,electroless coatings, plasma or thermal spray coatings, and physicalvapor deposition coatings. These coating technologies are generally moreexpensive than is hard chromium coating, but can mitigate the negativeenvironmental issues associated with hard chromium. The mainrequirements for the coating used in rework/rebuild operations are thatit be deposited to sufficient thickness, that it have the desiredsurface properties (i.e., resistance to corrosion, abrasion, erosion,wear, fatigue, etc.), that it adhere to the base material of thesubstrate component, and that it can be machined by a suitable method toexhibit the correct geometry.

Other factors may influence the choice of a coating technology for usein rework/rebuild operations. For example, the geometry of the componentmay preclude some coating technologies. Plasma spray coatings are notgenerally useful for coating internal diameters of bores or otherre-entrant geometries, and so could not be used for rework/rebuildexcept for regions of the component material that may be connected by aline-of-sight to the spray nozzle. Similarly, hard chromium plating isoften said to be a “low throwing-power” process, meaning that theprocess preferentially deposits chromium on portions of the componentcloser to a line-of-sight with a nearby plating anode. Many anodes areoften used in parallel to improve the density of “sight lines” to thecomponent and provide a uniform coating, but the coating of recesses,internal surfaces, and reentrant geometries is often non-uniform. Forthese reasons, rework/rebuild operations on complex surfaces aregenerally more challenging than those on simpler geometries.

Accordingly, a need has long existed for coatings, coating materials,and coating application processes to be used in rework/rebuildoperations that would provide the following: high strength and hardness,high corrosion resistance, high wear and abrasion resistance,thicknesses of at least 200 μm, improved environmental impact, improvedworker safety, improved cost, improved ability to coat geometries withinternal surfaces and non-line-of-sight surfaces, better compatibilityor matching of the substrate material to the rework/rebuild coating,improved surface properties, the ability to withstand subsequentmachining operations, and the ability to utilize existing electroplatingequipment.

SUMMARY OF THE INVENTION

The present invention relates to methods for the use of nanocrystallineor amorphous metals or alloys as coatings by industrial processes. Oneof the preferred embodiments provides a method for coating manycomponents with a nanocrystalline or amorphous metal or alloy, using ahigh volume electrodeposition process such as barrel plating and thecomponents produced thereby. Another preferred embodiment provides amethod for application of a nanocrystalline or amorphous coating in acontinuous electrodeposition process and the product produced thereby.Another of the preferred embodiments of the present invention provides amethod for reworking and/or rebuilding components and the componentsproduced thereby.

These and other features of the present invention are discussed orapparent in the following detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates a front view of a high volume electrodepositionapparatus suitable for the simultaneous coating of many parts in a highvolume process.

FIG. 2 illustrates a front view of an apparatus suitable for thecontinuous electrodeposition of a coating.

FIG. 3 illustrates a side view of a worn component in need ofrework/rebuild.

FIG. 4 illustrates a side view of a component in need of rework/rebuildafter a coating has been applied.

FIG. 5 illustrates a side view of a component after completion ofrework/rebuild.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Disclosed herein are methods for the implementation of nanocrystallineand amorphous metals and alloys as coatings. Specifically, three methodsfor implementation have been described: the simultaneous coating of manyparts in a high volume electrodeposition process, the continuouselectrodeposition of a coating, and the rework/rebuild of a componentusing a coating.

Nanocrystalline metal refers to a metallic body in which thenumber-average size of the crystalline grains is less than onemicrometer. The number-average size of the crystalline grains providesequal statistical weight to each grain. The number-average size of thecrystalline grains is calculated as the sum of all spherical equivalentgrain diameters divided by the total number of grains in arepresentative volume of the body. Amorphous metal refers to a metallicbody without long-range crystalline order, i.e., a metallic body whichis solid but not crystalline. A metallic body which comprises regions ofcrystalline structure in addition to the amorphous regions isadditionally included in the definition of an amorphous metal.

Nanocrystalline and amorphous metals and alloys are generally regardedas advanced structural materials, because as a materials class they tendto exhibit high strength, high abrasion resistance, high hardness, andother desirable structural and functional properties. Many technologiescan be used to prepare nanocrystalline or amorphous metals or alloys,including some which naturally yield coatings. For example,electrodeposition processes can be used to synthesize nanocrystalline oramorphous metal or alloy coatings on electrically conductive surfaces. Acoating produced by electrodeposition may be made in nanocrystallineform by many techniques, including addition of grain refining additives,deposition of an alloy that takes a nanocrystalline form, use of pulsedcurrent, or use of reverse pulsed current. Recent technologies aroundthe use of electrodeposition allow for precise control of the grain sizein a nanocrystalline metal or alloy, which is desirable to adjustcoating properties to the needs of a particular application.

Electrodeposition is commonly carried out in aqueous fluids, but is notrestricted to aqueous systems. For example, the electrodeposition bathcan comprise molten salts, cryogenic solvents, alcohol baths, etc. Anytype of electrodeposition bath can be used in conjunction with thepresent inventions.

Electrodeposition involves the flow of electrical current through thedeposition bath, due to a difference in electrical potential between twoelectrodes. One electrode is commonly the component or part which is tobe coated. The process may be controlled by controlling the appliedpotential between the electrodes (a process of potential control orvoltage control), or by controlling the current or current density thatis allowed to flow (current or current density control). The control ofthe process may also involve variations, pulses, or oscillations of thevoltage, potential, current, and/or current density. The method ofcontrol can also be a combination of several techniques during a singleprocess. For example, pulses of controlled voltage may be alternatedwith pulses of controlled current or current density. In general, duringan electrodeposition process an electrical potential exists on thecomponent to be plated, and changes in applied voltage, current, orcurrent density result in changes to the electrical potential on thecomponent. Any such control methods can be used in conjunction with thepresent inventions.

Nanocrystalline and amorphous metal or alloy coatings are unique andoffer desirable properties. The implementation of these materials andcoatings in practical applications requires relevant methods ofproduction for industrial applications. Thus, there is a need for newapplications of nanocrystalline or amorphous metal or alloy coatings,especially those prepared by electrodeposition.

One specific method to control the grain size of electrodepositednanocrystalline metals or alloys was presented by Detor and Schuh, inU.S. patent application Ser. Nos. 11/032,680 and 11/147,146, which arefully incorporated herein by reference. This method consists ofcarefully controlling the composition of an alloy deposit, which in turnallows for control of nanocrystalline grain size. For example, inelectroplated alloys of Ni—W, Ni—P, and many others, there is a simplerelationship between grain size and composition. In these cases higher Wor P contents are correlated with finer nanocrystalline grain sizes.Control of the W or P level therefore allows one to tailor the grainsize in the nanocrystalline range. Sufficiently high levels of W or P,in these examples, can lead to amorphous structures. The method of Detorand Schuh is to manipulate the electrodeposition process to control thecomposition, and thereby control the grain size in the nanocrystallineor amorphous deposit.

A specific application of the above method of Detor and Schuh is basedon reverse pulsed current during the process. Reverse pulsing of thecurrent allows control of the coating composition, and thereby allowscontrol of grain size. This reverse pulse technique can produce coatingsof tailorable grain size with reduced macroscopic defects such as cracksor voids.

This reverse pulsing technique involves the introduction of a bipolarwave current, with both positive and negative current portions, duringthe electrodeposition process. Using this technique provides the abilityto adjust the composition of the deposit, its grain size, or both withina relatively quick amount of time, and without changing either thecomposition or temperature of the electrodeposition bath liquid.Further, the technique produces high quality homogeneous deposits with alesser degree of voids and cracks than is conventionally achieved. Thetechnique also enables grading and layering of nanocrystalline crystalsize and/or composition within a deposit. Additionally, the technique iseconomical, scalable to industrial volumes, and robust.

It is possible to produce a variety of metals and alloys withnanocrystalline or amorphous structures using electrodeposition. Forexample, Ni—W alloys can be electrodeposited. Nanocrystalline oramorphous metals and alloys can be produced with a variety of differentelemental compositions in an electrodeposition process with a variety ofaverage grain sizes in the nanocrystalline range, and can be produced asan amorphous metallic form as well. As well, many Ni-based alloysincluding Ni—W, Ni—Mo, Ni—P, Ni—B, Ni—Fe, Ni—Co, Ni—S, and others can beelectrodeposited in nanocrystalline or amorphous form. The inventionsreported herein specifically apply to these electrodeposited metals andalloys in nanocrystalline or amorphous form, and to others as well.Co-based alloys such as Co—Mo, Co—W, Co—P and others are also possible,as are iron, copper, tin, cadmium, and zinc-based systems. Individualsskilled in the art will recognize many other metals or alloys, bothcommercial and experimental, which can be electrodeposited innanocrystalline or amorphous form. The present invention may be usedwith any such existing metals or alloys, or new systems that may bedeveloped in the future.

The present inventions also apply to composite systems, in which ananocrystalline or amorphous metal or alloy is combined with additionalphases. For example, hard particulates of metal, ceramic, intermetallic,or other material might be incorporated into a nanocrystalline oramorphous metal or alloy. Other potential phases which may beincorporated will also be recognized by those skilled in the art, suchas solid lubricant particles of graphite or MoS₂. Nanocrystalline andamorphous phases may also coexist in a single electrodeposited coating,which represents another composite structure which is a straightforwardvariation that may be used in the present invention.

Nanocrystalline and amorphous metals and alloys can also exhibit a widerange of properties, depending upon their composition and structure. Ofimportance in this regard is a method which allows the grain size to betailored, allowing the coating properties to be controlled in a mannerthat is desirable both for the functionality of the final coating, andfor optimization of a high volume production process like barrelplating. For example, high electrical conductivity is desirable inbarrel plating or other high volume electrodeposition processes, and bytailoring the grain size of a nanocrystalline deposit the conductivitymay be increased to acceptable levels to permit efficient high volumeproduction.

A particular method of producing a nanocrystalline or amorphous metal oralloy, and controlling and tailoring the grain size in the coating, isthe method outlined by Detor and Schuh above. In this method thecomposition of the coating is tailored to control the grain size of thenanocrystalline deposit. This may be accomplished by many techniques,including, for example, the use of periodic reverse pulses that tailorthe composition and grain size of the deposit.

Because electrodeposition processes can be adjusted to yieldnanocrystalline or amorphous metal or alloy coatings using technologiessuch as those described above, there are potential industrialapplications that will benefit from the improved properties of suchcoating materials.

High Volume Electrodeposition:

An invention disclosed herein is a method to simultaneously coat manycomponents using a high volume electrodeposition process, using ananocrystalline or amorphous metal or alloy coating. A related inventionis a component that has been coated with a nanocrystalline or amorphousmetal or alloy using a high volume electrodeposition process.

One industrial coating process in use in the electrodeposition orelectroplating industry pertains to the rapid, low-cost coating of manycomponents simultaneously. FIG. 1 illustrates a front view of a highvolume electrodeposition apparatus 100 suitable for this simultaneouscoating of many components 102 in a high volume process. The high volumeelectrodeposition apparatus 100 includes components 102, a componentvessel 104, an electrodeposition bath 106, a component terminal 108, anelectrical power supply 110, component electrical lead 112, a counterterminal 114, a suitable counter electrode 116, a counter electricallead 118, a bath vessel 120, an oil bath 122, an oil bath vessel 124, athermal controller 126, a heater 128, sensors 130, a compositionadjustment module 132, a stirring apparatus 134, a moving stirrer 136,an agitation motor 138, and an agitation drive unit 140.

Such high volume electrodeposition operations are often carried out in aso-called barrel plating operation, in which many components 102 to becoated are placed into a component vessel 104, which contains or iscontained within an electrodeposition bath 106. Some or all of thecomponents 102 in the component vessel 104 are in contact with theelectrodeposition bath 106, and the components 102 are all in electricalcontact with one another in the vessel. The components 102 are furtherelectrically connected to the component terminal 108 of an electricalpower supply 110 through a component electrical lead 112, which is incontact with one or more of the components 102, but not necessarily allof the components 102.

The component electrical lead 112 can take many forms, and in generalcan be considered an assembly of parts in electrical contact with oneanother, whose function is to channel electric current to components.The component electrical lead 112 can be a conductive wire such as ametal wire, or a series of metal wires in electrical contact with oneanother. The component electrical lead 112 can also be a conductive rodor other geometry of conductive material, or an assembly of many suchgeometries. In some cases, functional geometries are part of thecomponent electrical lead 112, as in the case of mechanical clips,clamps, screws, hooks, or brushes which facilitate electrical contactwith components. The component electrical lead 112 need not bestationary, but can move due to the agitation of the process. Forexample, the component electrical lead 112 can be part of a rotatingcomponent vessel 104.

Electrical current passes from the electric power supply 110, throughthe component terminal 108, through the component electrical lead 112,and into the components 102 with which it is in contact, to the othercomponents 102 via the physical contacts between the components 102. Theother terminal of the electrical power supply 110 is the counterterminal 114 and is connected to a suitable counter electrode 116through the counter electrical lead 118. The suitable counter electrode116 is present in the electrodeposition bath 106 but does not contactthe components 102 to be coated.

When electrical current is permitted to flow in this operation, providedthat the conditions of the operation are appropriate forelectrodeposition, metal ions in the electrodeposition bath 106 aredeposited or plated onto the various components 102 that are in thecomponent vessel 104, over the portions of the components 102 surfaceswhich are immersed in the electrodeposition bath 106. In this way, allof the components may be coated at the same time, as they are all partof a single electrode “system” that comprises many components 102.

The electrodeposition bath 106 is contained within the bath vessel 120.The bath vessel 120 sits within the oil bath 122, which is containedwithin the oil bath vessel 124. The thermal controller 126 is connectedelectronically to the heater 128, which extends into the oil bath 122.The temperature of the oil bath 122 is used to control the temperatureof the electrodeposition bath 106. The heater 128, which is controlledby the thermal controller 128, heats the oil bath 122. There are manypossible ways to control and maintain the proper temperature of theelectrodeposition bath 106. The heater 128 can be directly placed in theelectrodeposition bath 106, ambient environmental conditions can beused, etc.

Sensors 130 also extend into the electrodeposition bath 106. The sensors130 include temperature, composition, pH, and viscosity measurementdevices. Additional or fewer measurement devices can be included assensors 130. A composition adjustment module 132 also extends in theelectrodeposition bath 106. The composition adjustment module addsmaterial to the electrodeposition bath based on data produced by thesensors 130. The sensors 130 also provide data used by the thermalcontroller 126.

It is often desirable for the electrodeposition bath 106 to be stirred.The stirring apparatus 134 creates a magnetic field which causesmovement of the moving stirrer 136, thereby stirring theelectrodeposition bath. Many methods exist for stirring theelectrodeposition bath 106. The stirrer can be driven by a mechanicalpower source, components or other apparatus devices can be moved, etc.Pumps can also create aggressive fluid flow in the electrodepositionbath 106 to achieve stirring of the electrodeposition bath 106.

As the coating process proceeds, the points of contact betweencomponents 102 allow transmission of electrical current between them,but they may also shield the contact points and regions in theirimmediate vicinity from being thoroughly coated. For this reason, suchbarrel plating operations generally require some agitation of thecomponents 102, to continuously re-locate the inter-component contactpoints as the coating process proceeds.

The agitation motor 138 is connected to and powers the agitation driveunit 140, which is connected to the component vessel 104. Movement ofthe agitation drive unit 140 causes movement of the component vessel104, which causes movement and agitation of the components 102.

The agitation can be achieved in many ways, such as by vibrating thecomponent vessel 104 and its contents (including the components 102), byrotating or revolving the vessel, moving a belt on which the parts restas is used in the Technic Tumbleplater process. Aggressive fluid flow ofthe electrodeposition bath 106 induced by pumps can also be used toagitate the components 102. Of such agitation methods, rotation of thevessel is most commonly employed. The component vessel 104 need not be abarrel, it can be any device capable of holding the components 102.

Agitation of the components 102 and/or component vessel 104 provides forredistribution of the electrical contact points between the variouscomponents 102, as well as the contact between some of the components102 and the component electrical lead 112 connected to the electricpower supply 110. It helps prevent non-uniform coating of the components102 near such contacts, and can also prevent the coating from forming apermanent bond between components 102 at their contact points. Agitationcan be carried out continuously or in shorter periods separated byperiods without agitation.

Agitation can have many other benefits for an electrodeposition coatingprocess. It can lead to detachment of undesirable gas bubbles fromcoating surfaces (e.g., hydrogen bubbles). Agitation can also serve tocycle some components into and out of the electrodeposition bath 106.Agitation can also affect the quality of the coated product, by leadingto such things as leveling and improved surface finish.

High volume electrodeposition processes such as barrel plating can beconducted in a batch mode, or in a continuous mode. In a continuousoperation some mechanism of introducing and removing components 102 at aregular rate is introduced.

Some or all of the components 102 in a high volume electrodepositionprocess can be partly or completely masked, as by a paint or tapeapplied to parts of the components 102 surface upon which no coating isdesired. Thus, although an entire individual component 102 is exposed tothe deposition fluid, the masked portions of the surface would not beinvolved in electrodeposition. In a system using agitation to relocateelectrical contacts between components 102, contacts with the maskedportions of a component 102 may not conduct electrically. In this case,some components 102 may be out of electrical contact for some period orperiods of time during the process. In general, agitation should besufficient to render these periods insignificant, or to insure thatsimilar total such periods are experienced by all components 102.

In design of a high volume electrodeposition process, it is importantthat the agitation process is not too severe. Severe agitation can causemechanical damage to the components 102 being coated, which may be smalland delicate.

High volume electrodeposition coating methods, such as the barrelplating process and Technic Tumbleplater Process, can be adapted to usevarious technologies to yield nanocrystalline or amorphouselectrodeposits. This would allow for high volume coating of componentswith nanocrystalline or amorphous coatings. Nanocrystalline andamorphous metals and alloys exhibit many of the desirable propertiesimportant to high volume or barrel plating. They are generally strongand resist contact damage, abrasion and wear; these properties aredesirable to avoid damage to the coating and the components during highvolume electrodeposition processing. Furthermore, the electricalconductivity of a nanocrystalline or amorphous metal or alloy may behigh, facilitating the passage of electrical current across contactsbetween components 102 or across the contact between a component 102 andthe component electrical lead 112 connected to the electric power supply110.

It is a preferred embodiment of the present invention to use the methodof Detor and Schuh for electrodepositing nanocrystalline or amorphousalloys or metals as coatings, using a high volume production processlike barrel plating or the Technic Tumbleplater process, and to induce adesired nanocrystalline grain size by controlling the composition of thedeposited alloy. Another embodiment of the invention uses the method ofDetor and Schuh where the composition of the deposit is controlled byusing a designed periodic reverse pulse process during deposition, inorder to control the grain size. By controlling and tailoring the grainsize, desired material properties in the coating can be achieved.

Continuous Electrodeposition:

An invention disclosed herein is a continuous electrodeposition processincluding the deposition of a nanocrystalline or amorphous metal oralloy coating. A related invention is the product coated by ananocrystalline or amorphous metal or alloy in a continuous process.

A high-volume electrodeposition processes based on continuouselectrodeposition is also in use in industry. FIG. 2 illustrates a frontview of a continuous electrodeposition apparatus 200 suitable for thecontinuous coating of a component strip 202 in a high volume process.The continuous electrodeposition apparatus 200 includes a componentstrip 202, a component coating 203, an electrodeposition bath 206, acomponent terminal 208, an electrical power supply 210, componentelectrical lead 212, a counter terminal 214, a suitable counterelectrode 216, a counter electrical lead 218, a bath vessel 220, an oilbath 222, an oil bath vessel 224, a thermal controller 226, a heater228, sensors 230, a composition adjustment module 232, stirringapparatus 234, and a moving stirrer 236.

Continuous deposition of a coating onto a component strip 202, such as astrip of metal, can be achieved if a continuous feed of the componentstrip 202 is traveling through the electrodeposition bath 206, and thecomponent strip 202 is made an electrode as in a conventional depositionprocess. Unlike a conventional electrodeposition process in which acomponent is dipped into the electrodeposition bath, continuousdeposition involves the component strip 202 traveling through theelectrodeposition bath 206 whereby a beginning portion of the componentstrip 202 enters the electrodeposition bath 206 before an adjoiningportion of the component strip 202 and the beginning portion of thecomponent strip 202 also exits the electrodeposition bath 206 before theadjoining portion of the component strip 202. As the component strip 202travels through the electrodeposition bath 206 the component coating 203is applied.

The component strip 202 to be coated enters the electrodeposition bath206, which contains or is contained within an electrodeposition bath206. A portion of the component strip 202 is in contact with theelectrodeposition bath 206. The component strip 202 is furtherelectrically connected to the component terminal 208 of an electricalpower supply 210, through a component electrical lead 212, which is incontact with the component strip 202. The component electrical lead 212includes anything used to contact with the component strip 202, such asa wire, rod, alligator clip, screw, clamp, etc.

Electrical current passes from the electric power supply 210, throughthe component terminal 208, through the component electrical lead 212,and into the component strip 202. The other terminal of the electricalpower supply 210 is the counter terminal 214 and is connected to asuitable counter electrode 216 through the counter electrical lead 218.The suitable counter electrode 216 is present in the electrodepositionbath 206, but does not contact the component strip 202.

When electrical current is permitted to flow in this operation, providedthat the conditions of the operation are appropriate forelectrodeposition, metal ions in the electrodeposition bath 206 aredeposited or plated onto the portion of the component strip 202 which isimmersed in the electrodeposition bath 206.

The electrodeposition bath 206 is contained within the bath vessel 220.The bath vessel 220 sits within the oil bath 222, which is containedwithin the oil bath vessel 224. The thermal controller 226 is connectedelectronically to the beater 228, which extends into the oil bath 222.The temperature of the oil bath 222 is used to control the temperatureof the electrodeposition bath 206. The heater 228, which is controlledby the thermal controller 228, heats the oil bath 222. There are manypossible ways to control and maintain the proper temperature of theelectrodeposition bath 206. The heater 228 can be directly placed in theelectrodeposition bath 206, ambient environmental conditions can beused, etc.

Sensors 230 also extend into the electrodeposition bath 206. The sensors230 include temperature, composition, pH, and viscosity measurementdevices. Additional or fewer measurement devices can be included thesensors 230. A composition adjustment module 232 also extends in theelectrodeposition bath 206. The composition adjustment module addsmaterial to the electrodeposition bath based on data produced by thesensors 230. The sensors 230 also provide data used by the thermalcontroller 226 used to control the temperature.

It is often desirable for the electrodeposition bath 206 to be stirred.The stirring apparatus 234 creates a magnetic field which causesmovement of the moving stirrer 236, thereby stirring theelectrodeposition bath. Many methods exist for stirring theelectrodeposition bath 206. The stirrer can be driven by a mechanicalpower source, components 102 or other apparatus devices can be moved,etc. Pumps can also create aggressive fluid flow in theelectrodeposition bath 206 to achieve stirring.

In a continuous process, the component strip 202 to be coated can travelthrough a stationary electrodeposition bath 206, or theelectrodeposition bath 206 may be translated along its length. Theelectrodeposition bath 206 need not be contained in a bath vessel 220,for example a traveling sprayed bath, which may or may not recirculatethe bath fluid, can be used. Both the electrodeposition bath 206 andcomponent strip 202 can also be in motion, provided that there is a netrelative motion of the electrodeposition bath 206 and component strip202 with respect to one another. A flexible component strip 202 can alsodeflect or curve to enter the electrodeposition bath 206 rather thantraveling straight through the electrodeposition bath 206.

Furthermore, the relative motion of the component strip 202 with respectto the bath need not be uninterrupted, smooth, or perfectly continuous.Periodic discrete advances of the component strip 202, for example,constitute a continuous process with an average feed rate given by thesum of the lengths of each advance divided by the sum of the dwell timesafter each advance and the sum of the times involved in each advance.Furthermore, periods of reverse relative motion of the component strip202 in the deposition bath 206 are possible and affect the average feedrate of the process, but do not limit the generality of the presentinventions.

The component strip 202 may be fed from one reel to another in acontinuous fashion, or part of a larger manufacturing operation.Additionally, the geometry of the component strip 202 is arbitrary insuch an operation. Component strips 202 such as Wires, rods, I-beams,sheets, perforated sheets or strips, extrusions, or even more complexgeometries can be coated in high volumes through a continuous process.

Part or all of the component strip 202 geometry can be coated. Bymasking or otherwise preventing current flow to some portions of thegeometry, it is possible to selectively coat, for example, one side of asheet or strip, one edge of a rectangular beam, or a length-wise grooveor raised feature on a complex geometry.

In continuous processes such as described above, the coating material ischosen for its desirable properties in the final coated product. Somedesirable properties may be high hardness, high strength, ductility,wear resistance, electrical properties, magnetic properties, corrosioncharacteristics, substrate protection, and many others.

Continuous electroplating operations can also be adapted to incorporatetechnologies that allow the deposition of nanocrystalline or amorphousmetals or alloys. Continuous operations include the coating of acontinuous feed of a component strip 202 or sheet of metal, where thecomponent strip 202 or sheet is made an electrode as in a conventionaldeposition process. Such component strip 202 may be fed from one reel toanother in a continuous fashion, or part of a larger manufacturingoperation with or without feeding reels. Additionally, the geometry ofthe component strip 202 is arbitrary in such an operation. Componentstrips 202 such as wires, rods, I-beams, sheets, perforated sheets orstrips, extrusions, or even more complex geometries can be coated inhigh volumes through a continuous process. Part or all of the geometrycan be coated in this manner. By masking or otherwise preventing currentflow to some portions of the geometry, it is possible to selectivelycoat, for example, one side of a sheet or strip, one edge of arectangular beam, or a length-wise groove or raised feature on a complexgeometry.

A continuous plating process can also be used to coat a series ofdiscrete components, which are assembled into a continuous strip. Forexample, a sheet of metal can be perforated into many individualcomponents that are connected to one another, and this connected stripof components moved through the deposition bath to coat the components.Individual components can also be assembled into a continuous strip bymany other methods that provide an electrical contact between componentsalong the length of the strip. For example, a traveling wire or cableupon which a series of hooks are affixed may be used to hang manycomponents, which travel through the deposition bath with the wire.Other continuous processes involving discrete components will beapparent to those skilled in the art, and any such processes may be usedin conjunction with the present invention.

In a preferred embodiment of the present invention, a continuouselectroplating operation is adapted to produce a nanocrystalline oramorphous metal or alloy coating, where the method of Detor and Schuhdescribed above is used to effect nanocrystalline grain size of adesired dimension, or an amorphous structure, in the coating material.In its most general form, the method of Detor and Schuh employs controlof the alloy composition of the coating to control the nanocrystallinegrain size. Another embodiment of the invention is to use the method ofDetor and Schuh via the application of a periodic reverse pulse tocontrol the coating composition and grain size, in a continuouselectrodeposition process.

Rework/Rebuild:

Another invention disclosed herein is a rework/rebuild process includingthe use of a nanocrystalline or amorphous metal coating. A relatedinvention is a component that has been reworked or rebuilt using ananocrystalline or amorphous metal coating.

Another use of electrodeposited coatings is for the reworking andrebuilding of components. The terms “rework” and/or “rebuild”,collectively—“rework/rebuild,” are defined herein to describe a processof depositing a coating material atop a substrate material or componentin order to bring the dimensions of the component to within a specifiedtolerance and/or repair surface defects in the component. Theseprocesses are also sometimes referred to as “remanufacturing” in theliterature.

FIG. 3 illustrates a side view of a worn component 302 in need ofrework/rebuild. The worn component 302 has a worn surface 304 which isneed of rework/rebuild. A worn surface 304 is one, which, owing to itsuse in service, has experienced abrasion, erosion, wear, corrosion, orany other such process or combination of processes that may tend toremove some material and consequently alter the shape of the component.A worn surface 304 can also be a result of the initial component 302manufacturing process.

FIG. 4 illustrates a side view of a worn component 302 in need ofrework/rebuild after a coating has been applied. Rework/rebuild is usedas a means of replenishing the worn material by first depositing freshmaterial in the form of an applied coating 402.

FIG. 5 illustrates a side view of a worn component 302 after completionof rework/rebuild. After the application of the applied coating 402,subsequent machining is performed on the applied coating 402, creating amachined surface 502. The machined surface 502 brings the worn component302 back to within an acceptable dimensional tolerance 504 of itsintended shape. Rework/rebuild might also be used to repair defects in amaterial that has not been put into service, but which developed defectsduring synthesis and processing stages, or perhaps developed suchdefects unintentionally by misuse or during handling or storage. Defectsformed during the application of a coating may also be reworked.

In some cases, the wear, abrasion, corrosion, or erosion that acomponent experienced may have involved the degradation not only of theworn component's 302 base material, but also of a coating materialpreviously applied to the component. In this case the rework/rebuildprocess often begins by removal (stripping) of the original coatingmaterial prior to the subsequent application of a new coating for thepurpose of rebuilding the component. Rework/rebuild can also apply tocomponents upon which the only wear or degradation occurred on a priorcoating layer, where only said coating layer requires rework.

Rework/rebuild can also be used on worn components 302 which underwent asurface degradation process that did not involve material removal, forexample oxidation, abrasion, or fatigue crack growth. In these cases,rework/rebuild can be preceded by a surface finishing process such asmachining, polishing, shot peening, chemical milling, etc. In this casethe rework process would rebuild material removed by the surfacefinishing process rather than that removed by virtue of abrasion orcorrosion in service.

Although rework/rebuild is a process most commonly applied to componentsthat experience mechanical loads (i.e., machine components or structuralcomponents), the process is quite general and may have application inmany other domains including for components with electrical, electronic,magnetic, anti-corrosive, optical, aesthetic, medical, or otherfunctional or decorative properties.

After the application of a suitable coating, a machining operation isoften used to form the coated component into a desirable geometry. Theterm ‘machining’ may refer to conventional machine shop operationsincluding milling, grinding, filing, or turning on a lathe, or can moregenerally refer to any process by which some of the coating material isremoved. This can include mechanical polishing, chemical polishing,combined mechanical-chemical polishing, electrochemical milling,electrochemical etching, or electro-chemical polishing.

In some instances, a machining operation is not required at all for arework/rebuild operation, if the deposited coating brings the geometryof the component to within the required dimensional tolerance withoutthe need for machining.

The rework/rebuild process includes three stages: surface preparation,coating, and machining. The first stage involves preparing the surfaceof the component to be reworked/rebuilt for the later coating. Thissurface preparation includes cleaning, removal (stripping) of anoriginal coating material, machining, polishing, shot peening, chemicalmilling, etc. Surface preparation is not always required and includesany operations which prepares the surface for further rework/rebuildprocessing. The second stage involves coating the surface of thecomponent to be reworked/rebuilt; an invention contained herein is touse a nanocrystalline or amorphous metal coating.

Nanocrystalline and amorphous metals are desirable for rework/rebuildoperations because they are generally very strong, hard, and can exhibitimproved abrasion and corrosion resistance as compared with their moreconventional microcrystalline counterparts (which have an averagecrystalline grain size above one micrometer).

Electrodeposition is a common technology for the application ofcoatings. Accordingly, existing electrodeposition equipment can be usedto apply the nanocrystalline and amorphous metallic coatings.

Coatings of 200 μm or thicker are generally required for rework/rebuildoperations. Nanocrystalline metal coatings greater than 200 μm inthickness can be produced by electrodeposition. Amorphous metals canalso be electrodeposited to the required high thicknesses forrebuild/rework, as explained in U.S. patent application U.S. Ser. No.11/032,680 by Schuh and Detor, which is included fully herein byreference.

Thus, electrodeposition can be used to produce nanocrystalline andamorphous coatings of the proper thickness and desirable properties fora rework or rebuild operation. They also generally have desirable highhardness and abrasion resistance, and can be machined, polished,electro-chemically milled, or otherwise treated to achieve a desirablefinal geometry. Electrodeposited nanocrystalline and amorphous metalsare therefore ideal for rework/rebuild operations.

A technique for the electrodeposition of nanocrystalline metals is thatof Detor and Schuh described above. This technique controls thecomposition of an alloy deposit in order to control the grain sizes of ananocrystalline or amorphous alloy. It is a preferred embodiment of thepresent invention to use the method of Detor and Schuh for the purposeof rebuild and rework.

Another embodiment of the invention is to use periodic reverse pulsingto control composition, and thereby to control grain size of ananocrystalline coating. This reverse pulse technique is particularlysuited for the purpose of rework and rebuild because it producescoatings of tailorable grain size without macroscopic defects such ascracks or voids.

This reverse pulsed technique involves the introduction of a bipolarwave current, with both positive and negative current portions, duringthe electrodeposition process. Using this technique provides the abilityto adjust the composition of the deposit, its grain size, or both withina relatively quick amount of time, and without changing either thecomposition or temperature of the electrodeposition bath liquid.Further, the technique produces high quality homogeneous deposits with alesser degree of voids and cracks than is conventionally achieved. Thetechnique also enables grading and layering of nanocrystalline crystalsize and/or composition within a deposit. Additionally, the technique iseconomical, scalable to industrial volumes, and robust.

Thus, the reader will see that this invention provides a method ofrework/rebuild and an article of that method that provides manybenefits. A nanocrystalline and/or amorphous metal coating forrework/rebuild provides: high strength and hardness, high corrosionresistance, high wear and abrasion resistance, thicknesses of at least200 μm, improved environmental impact or worker safety as compared withprior art (e.g., when using a Ni-based, Co-based or Cu-basednanocrystalline or amorphous metal instead of hard chromium), improvedcost (e.g., when using an electrodeposited nanocrystalline or amorphouscoating instead of a physical vapor deposited or plasma sprayedcoating), improved ability to coat geometries with internal surfaces andnon-line-of-sight surfaces (e.g., when using a high throwing-powerelectrodeposition process for a nanocrystalline or amorphous Ni-basedalloy, as compared with a line-of-sight process such as plasma spraycoating or a lower throwing-power electrodeposition process such as hardchromium plating), better compatibility or matching of the substratematerial to the rework/rebuild coating (e.g., if a nanocrystalline oramorphous Ni-based coating is used atop a nickel based alloy for bettermatching of the elastic properties, as compared with the use of hardchromium atop the nickel based alloy, which have different elasticproperties), improved surface properties (e.g., if a nanocrystalline oramorphous form with better corrosion resistance is used instead of hardchromium), ability to withstand subsequent machining operations, and theability to utilize existing electroplating equipment.

While the above description contains much specificity, these should notbe construed as limitations on the scope of the invention but rather asan explanation of one preferred embodiment thereof. Many othervariations are possible. Accordingly the scope of the invention shouldbe determined not by the embodiments illustrated but by the appendedclaims and their legal equivalents.

Partial Summary:

Inventions disclosed and described herein include methods for the use ofnanocrystalline or amorphous metals or alloys as coatings by industrialprocesses. Processes of manufacture using such coatings are described,as are products incorporating or using such coatings.

Thus, this document discloses many related inventions.

One invention disclosed herein is an article of manufacture comprising ananocrystalline or amorphous material applied to a component, wherebythe nanocrystalline or amorphous material is applied through anelectrodeposition process where an electric potential exists on thecomponent through an electrical contact with other components.

The electrodeposition process may be tailored to produce a specificgrain size. The electrodeposition process may also be tailored to applymaterial with more than one grain size, or with varying composition orgrain size.

According to one preferred embodiment, the article of manufacturecomprises a nanocrystalline or amorphous material applied to acomponent, whereby the nanocrystalline or amorphous material is appliedthrough an electrodeposition process where an electric potential existson the component through an electrical contact with other components,and the process uses a vessel to hold multiple components.

According to another set of preferred embodiments, the electrodepositionprocess involves an electrical potential having periods of both positivepolarity and negative polarity, or in which the electrodepositionprocess involves an electrical potential that is pulsed more than once.

A related set of preferred embodiments involves the deposition of ananocrystalline or amorphous Ni-based coating containing one of theelements W, Mo, P, or B, in conjunction with an electrical potentialhaving periods of both positive and negative polarity, or in which theelectrodeposition process involves an electrical potential that ispulsed more than once.

In yet another preferred embodiment, the article of manufacturecomprises a nanocrystalline or amorphous material applied to acomponent, whereby the nanocrystalline or amorphous material is appliedthrough an electrodeposition process where an electric potential existson the component through an electrical contact with other components,and where the electrical contact with other components is changing as aresult of agitation of the components.

Another invention disclosed herein is an article of manufacturecomprising a nanocrystalline or amorphous metal applied to a componentwhereby the nanocrystalline or amorphous metal is applied through anelectrodeposition process with a beginning portion of the componententering the electrodeposition bath before an adjoining portion of thecomponent and the beginning portion of the component also exiting theelectrodeposition bath before the adjoining portion of the component.

The electrodeposition process may be tailored to produce a specificgrain size. The electrodeposition process may also be tailored to applymaterial with more than one grain size, or with varying composition orgrain size.

The electrodeposition process may involve an electrical potentialexisting on the component.

According to a set of preferred embodiments, the article of manufacturecomprises a nanocrystalline or amorphous metal applied to a componentwhereby the nanocrystalline or amorphous metal is applied through anelectrodeposition process with a beginning portion of the componententering the electrodeposition bath before an adjoining portion of thecomponent and the beginning portion of the component also exiting theelectrodeposition bath before the adjoining portion of the component,and the electrodeposition process involves an electrical potentialhaving periods of both positive polarity and negative polarity, or inwhich the electrodeposition process involves an electrical potentialthat is pulsed more than once.

A related set of preferred embodiments involves the deposition of ananocrystalline or amorphous Ni-based coating containing one of theelements W, Mo, P, or B, in conjunction with an electrical potentialhaving periods of both positive and negative polarity, or in which theelectrodeposition process involves an electrical potential that ispulsed more than once.

Still another invention disclosed herein is an article of manufacturecomprising a nanocrystalline or amorphous material applied to acomponent for a purpose of repairing damage to a component surface orbringing the geometry of the component to within a desired dimensionalsize.

The application of a nanocrystalline or amorphous metal can comprise anelectrodeposition process. The application of a nanocrystalline oramorphous metal can also comprise an electrodeposition process tailoredto produce a specific grain size, or tailored to apply material withvarying composition or grain size.

In a set of related preferred embodiments, the application of ananocrystalline material comprises an electrodeposition process with anelectrical potential having periods of both positive polarity andnegative polarity, or where the electrical potential is pulsed more thanonce.

A related set of preferred embodiments involves the deposition of ananocrystalline or amorphous Ni-based coating containing one of theelements W, Mo, P, or B, in conjunction with an electrical potentialhaving periods of both positive and negative polarity, or in which theelectrodeposition process involves an electrical potential that ispulsed more than once.

In a final preferred embodiment, an article of manufacture comprises ananocrystalline or amorphous material applied to a component for apurpose of repairing damage to a component surface or bringing thegeometry of the component to within a desired dimensional size, wherethe component surface receives subsequent processing to bring thegeometry of the component to within a desired dimensional size.

1. An article of manufacture comprising: a component having at least onesurface; and a nanocrystalline or amorphous material applied to the atleast one surface whereby the nanocrystalline or amorphous material isapplied through an electrodeposition process where an electric potentialexists on the component through an electrical contact with at least oneother component.
 2. The article of manufacture of claim 1 where theelectrodeposition process is tailored to produce a nanocrystallinematerial having a specific grain size.
 3. The article of manufacture ofclaim 1 where the electrodeposition process is tailored to apply ananocrystalline or amorphous material with varying compositions or grainsizes.
 4. The article of manufacture of claim 1 where theelectrodeposition process uses a vessel to hold the component and the atleast one other component.
 5. The article of manufacture of claim 1where the electrodeposition process involves an electrical potentialhaving periods of both positive polarity and negative polarity.
 6. Thearticle of manufacture of claim 1 where the electrodeposition processinvolves an electrical potential that is pulsed more than once.
 7. Thearticle of manufacture of claim 1 where the electrical contact with theat least one other component is changing as a result of agitation of thecomponent and the at least one other component.
 8. An article ofmanufacture comprising a nanocrystalline or amorphous material appliedto a component whereby the nanocrystalline or amorphous material isapplied through an electrodeposition process with a beginning portion ofthe component entering an electrodeposition bath before an adjoiningportion of the component entering the electrodeposition bath and thebeginning portion of the component also exiting the electrodepositionbath before the adjoining portion of the component exiting theelectrodeposition bath.
 9. The article of manufacture of claim 8 wherethe electrodeposition process is tailored to produce a nanocrystallinematerial having a specific grain size.
 10. The article of manufacture ofclaim 8 where the electrodeposition process is tailored to apply ananocrystalline or amorphous material with varying compositions or grainsizes.
 11. The article of manufacture of claim 8 where theelectrodeposition process involves an electrical potential havingperiods of both positive polarity and negative polarity.
 12. The articleof manufacture of claim 8 where the electrodeposition process involvesan electrical potential that is pulsed more than once.
 13. The articleof manufacture of claim 8 where an electric potential exists on thecomponent.
 14. An article of manufacture comprising: a component havingat least one surface; and a nanocrystalline or amorphous materialapplied to the at least one surface for a purpose of repairing damage tothe at least one surface or bringing a geometry of the at least onesurface to within a desired dimensional size.
 15. The article ofmanufacture of claim 14 where an electrodeposition process is used toapply the nanocrystalline or amorphous material to the at least onesurface.
 16. The article of manufacture of claim 15 where theelectrodeposition process is tailored to produce a nanocrystallinematerial having a specific grain size.
 17. The article of manufacture ofclaim 15 where the electrodeposition process is tailored to apply thenanocrystalline or amorphous material with varying compositions or grainsizes.
 18. The article of manufacture of claim 15 where theelectrodeposition process has an electrical potential having periods ofboth positive polarity and negative polarity.
 19. The article ofmanufacture of claim 15 where an electrical potential is pulsed morethan once.
 20. The article of manufacture of claim 14 where thecomponent surface receives subsequent processing to bring the geometryof the component to within the desired dimensional size.